Esters



Patented June 6, 1944 ESTERS Donald J. Loder, Wilmington, and Wilber 0. Teeters, Roselle, Del., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application June 14, 1940, Serial No. 340,473

' 13 Claims.

The present invention relates to new materials and to methods for their preparation, and more particularly, to the polyhydric alcohol esters of alkoxy and alkoxy methylene substituted acetic acids and methods for their preparation. The application is a continuation in part of our copending application S. N. 272,134, filed May 6, 1939, now Patent No. 2,290,128.

An object of the present invention is to provide new compositions of matter and processes for their preparation. A further object of the invention is to provide monoand poly-ethylene glycol and monoand di-glycerol and triglyceryl esters of substituted glycolic acids, together with processes for their preparation. Yet another ob ject of the invention is to provide a process for the preparation of glycol monoand di-glycolates and glycerol monoand di-glycolates by esterifying substituted glycolic acid with glycols and glycerol, respectively. A further object of the invention is to provide monoand di-substituted glycolic acid esters of ethylene glycol and polyethylene glycols and the mono-, diand tri-glycerides of substituted glycolic acids, together with processes for their preparation. Other objects and advantages of the invention wil hereinafter appear.

These objects, as well as others which will be apparent as the description proceeds, may be accomplished by reacting a lower alkyl ester of an oxy-substituted acetic acid with a polyhydric alcohol under conditions favorable to the interchange of alcohol radicals. This interchange of alcohol radicals is effected by heating the alcohol and ester together, preferably in the presence of alkaline alcoholysis catalysts. The ester interchange proceeds more readily if the alcohol selected for reaction with the ester boils at a higher temperature than the alcohol liberated by the interchange, because the latter alcohol is then more readily removed from the zone of reaction, for example, by distillation.

The ester interchange process described above may be employed for the preparation of either the monoglycolates or the polyglycolates, for example, when it is desired to prepare ethylene glycol monoglycolate, in accord with the ester interchange process, equimolecular proportions of the ester and ethylene glycol are reacted. If, on the other hand, the reaction mixture contains two moles of the ester per mole of the ethylene glycol and the reaction continues to completion, the product will be ethylene glycol diglycolate. In like manner, if it is desired to obtain a glycerol monoand di-glycolate or glyceryl triglycolate,

one mole of glycerol is reacted with one, two, or three moles of an ester of glycolic acid. The process is applicable generally to the preparation of polyhydric alcohol, monoand poly-glycolates, monoand polyalkoxy glycolates and monoand poly-alkoxy methoxy glycolates from the polyhydric alcohols and the lower alkyl esters of, respectively, glycolic acid, CH2(OH) COOH, alkoxy acetic acids, CH2(OR) COOH, such as methoxy acetic acid, CH2(0CHa)COOH, and alkoxy methoxy acetic acids,

CH2 (OCHzOR) COOH, such as methoxy methoxy acetic acid,

CH2 (OCI-IzOCHs) COOH.

The methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, etc. esters of this acid, may be reacted with the polyhydric alcohols generally, such, for example, as: the glycols, e. e., ethylene glycol, propylene glycol, butylene glycol, amylene glycol, diethylene glycol, trimethylene glycol, octadecanediol, tetramethylene glycol, hexamethylene glycol, or the alcohols containing more than two hydroxyl groups, such as glycerol, diglycerol, triglycerol, trimethylol .methane and trimethylol propane; sugars, such as, dextrose, sucrose, xylose, galactose, fructose, maltose, and mannose; and the sugar alcohols, such as, sorbitol, mannitol, and dulcitol; as well as castor oil (glyceryl triricinoleate), hydrogenated castor oil, (hydroxy stearin) and like long chain polyhydric alcohols.

This invention likewise includes esters of glycolic acid, alkoxyand alkoxy methoxy-acetic acids with ether alcohols, i. e., polyhydric alcohols having at least one free hydroxyl group, one or more hydroxyl groups being etherified. Examples of such ether alcohols include the monoalkyl ethers of ethylene glycol, such as the monomethyl, -ethyl, -propyl or -butyl ethers of ethylene glycol, propylene glycol, etc. Esters of this class would be, e. g., ethylene glycol monomethyl ether glycolate, ethylene glycol monoethyl ether glycolate, ethylene glycol monomethyl ether methoxy acetate, CH2 OCH3 COOCI-IzCHzOCHs, and ethylene glycol monomethyl ether methoxy methoxy acetate,

CH2 (ocHaocrn) COOCH'zCHzOCHa.

The monoand di-glycolates of the monog1ycerides are likewise included, e. g., the monoglycolates of the monoglycerides,

CH2 (OH) COOCHzCI-IOI-LCl-IzOR in which R is methyl, ethyl, propyl, butyl, etc.

The monoglycerides of stearic acid, oleic acid, palmitic acid, etc. may be used for the preparation of these monoand di-glycolates.

Polyhydric alcohol esters as well as ether alcohol esters of substituted glycolic acids may likewise be prepared by the aforesaid ester interchange process. For example, such esters of the following acids are also included in the present invention: the alkoxy acetic acids,

CI-I2(OR) COOH, e. g. ethoxy-, propoXy-, isobutoxy-acetic acids, etc.; the alkoxy alkoxy acetic acids: CH2(OROR) coon, 5"

e. g., ethoxy methoxy-, propoxy methoxy-, isobutoxy methoxy-acetic acids, etc.; and the alkoxy carbomethoxy methoxy acetic acids,

CH2 (OCHZOCHQCOOR) COOH,

e. g., methoxy carbomethoxy methoxy acetic acid or ethoxy carbomethoxy methoxy acetic acid, which may be prepared by reacting glycolic acid formals with'carbon monoxide in accord with the process described in the copending application of SJ-N; 256,854, filed February 17, 1939. 0

The'esters-of the present invention' are preferably prepared by the above described ester interchange process,- for 'the'reason that this process provides 'a' means-of obtaining both the monoand'pol-y-glycolates inexcellent' purity and yield.

Simple esterification maybe employed, however,

drating characteristics of glycolic'acid, it does not react readily with glycerol butforms acrolein at the expense of the glycerol ester, and, conseof sodium in 7 grams of methanol (30% sodium methoxide solution). This mixture was refluxed underafractionating column, fitted with a distilling head arranged for controlled reflux, until the head temperature had receded to (Se-65 C. The methanol was removed as rapidly as possible at the head of the column, the head temperature being carefully maintained between 64 C. and 66 C. The refluxing and the collecting of the methanol were continued for approximately ten hours, at the end of which time approximately 860 grams (25 moles) of methanol had been collected.

The heat was discontinued and any low boiling material which remained was removed by vacuum distillation. (If desired the color of the product may be improved by treatment with 2 per cent of its weight of a standard decolorizing charcoal. For most purposes, however, the color of the untreated ester was satisfactory.)

(B) To 310 parts, (5 moles) of ethyleneglycol,v

containedin, a suitable 3-necked flask equipped with an efiicientstirrer. and reflux condenser, was-s In both (A) and (B) the reaction mixture .was cooled; andt-he product obtained was a pale.

amber-colored liquid which contained 9.8 to 99 per cent. of glycol monoglycolate. substantially;quantitative. based on either the glycol or glycolate; sp. gr. Was 1,283 F./ 60 F.

' and the saponification number was 460.

quently,;simple ,esterification should preferably. 7

not Jae qemployed when the glycerol .esters of glycolicfacid are desired. V

Theinvention likewise provides another. ester interchangeprocess for the preparation of esters of glycolic acid... This process involves theinteraction; of a..p olyhydric. alcohol or ether-1 alcohol with glycolide,.,which.may be considered to be a poly-ester of glycolic acid. This reaction maybe effected by firstforming the glycolide (prepared,

e. g in/the usual manner by heating the glycolic.

acid to driveoff all the water), and subsequently reactingthe glycolide (whichmay be present, as a diglycolide, or as apolyglycolide) with the polyhydric alcohol.

If a partially dehydrated .gly-m colic acid;is,used,.e. g., a diglycolide or polyglycolidein the presence of free glycolic acid, the

initial ,reactionis carried out under reflux and then waterof esterification, of free glycolic acid and glycol removed with the aid of heat, either with or without awater carrier, such as, toluene.

Ordinarily,.,this ester interchange maybe conducted under ,atmospheric pressure, particularly with the higher boiling polyhydric alcohols, al-

though ;if low boiling alcohols are employed, autogenous pressure or applied pressures of from 5 to 600 atmospheres may be employed.

The more detailed practice of the inventionis illustrated by the following examples in which parts given are by weight unless otherwise stated. There are, of course, many forms of the invention other than these specific embodiments.

EXAMPLE I.;-ETHYLENEGLYCOL Mono GLYCOLATE' ene glycol and, as catalyst, a solution.of.3.0 grams.

EXAMPLE II.ETHYLENE DIGLYCOLATE Yield quantitative.

Amber .colored. viscous liquid. Sp. gr. .1.327/.20"./4,

Sap. No. 611.3.

EXAMPLE III.-GLYCEROL MONOGLYCOLATE Methyl glycolate; 1980 parts, 22 moles Glycerol (96%) 2108 parts, 22 moles Anhydrous potassium car bonate;(catalyst) 10 parts Methanol off .704 parts, 22 moles 1' Product 1 Yieldiquantitativa.

Pale amber. colored. liquid. Sp. gr. 1.320 60/60 F. Sap. No. "380.

EXAMPLE I'V.-'-'G!,CEROL DIGLYCOLATE The conditions and procedure are the same as for Examplel; j x

The yield was Products from (A) and (B) are identical in constants.

Yield substantially quantitative in both cases. Amber colored viscous liquid.

Sp. gr. 1.393 /4.

Sap. No.542.

EXAMPLE V.BETA-ETHOXY ETHYL GLYCOLATE Up to and through the removal of methanol the conditions are the sam as Example I.

Quantities Methyl glycolate 990 parts, 11 moles Beta-ethoxy ethanol (Cellosolve) 900 parts, 10 moles Catalyst:

-1 part Na in 4 parts methanol Anhydrous potassium carbonate 5 parts Methanol on 309 parts, 9.7 moles The refluxing and the collecting of the methanol were continued until no more methanol was liberated. The reaction mixture was cooled'and the calculated quantity of concentrated sulfuric acid added to form the neutral sulfate salt. The neutralized product was vacuum distilled and the beta-ethoxy ethyl glycolate distilled, giving 75 to 90% yield. It Was found to be a. mobile, colorless liquid having the following constants:

B. P. 162-163 C./ 120 mm.; Sap. No. theoretical 378; found 375.

EXAMPLE VI.BETA-METHOXY E'I'HYL GLYCOLATE To a mixture of 760 parts (10 moles) of crystalline glycolic acid and 760 parts (10 moles) of beta-- methoxy ethanol was added 2 parts of concentrated sulfuric acid and parts of benzene (water carrier). The reaction mixture was heated to reflux temperature and the water of esterification, which separated as a lower layer in a suitable decanting type distilling head, was removed. When the distillate no longer formed two layers the heat was discontinued and the crude ester cooled. The acid catalyst present in the crude mixture was exactly neutralized with anhydrous potassium carbonate and the beta-methoxy ethyl glycolate distilled and recovered in a yield of to It was recovered as a mobile, colorless liquid-having a B. P. of 155-156/135 mm.; a sp. gr. of 1.163 60/60 F. and a saponification No. of 417.

EXAMPLE VIL-Ocranaomsmor. DIGLYCOLATE The procedure was the same as in Example I with the following exceptions: isobutanol, instead of methanol, was distilled off at th head of the column, at -110"; the reaction mixture was blanketed with nitrogen and a slow stream of this gas was'continuously passed over the surface during the ester interchange; the pot temperature was held between 160-170 throughout the reaction; the product was filtered hot to give a quantitative yield of the ester.

Quantities octadecanediol 429 parts, 1.5 moles Isobutyl glycolate 396 parts, 3.0 moles Sodium methoxide (30%) (catalyst) 6 parts Product White low melting solid. Sap. No. theoretical 194; found 184.

EXAMPLE VIII.CASTOR OIL GLYCOLATE Procedure the same as for octadecanediol diglycolate, Example VII.

Quantities Castor oil 888 parts, 1 mole Isobutyl glycolate 396 parts, 3 moles Sodium methoxide (catalyst) 3.0 parts of 30% in methanol Product Yield substantially quantitative.

Amber reddish viscous liquid. Sap. No. 242.

EXAMPLE IX.ETHYLENE GLYcoL MONOME'IHOXY ACETATE Procedure the sam as Example I (glycol monoglycolate) with the exception that, after the reaction mixture was cooled, the alkaline catalyst was exactly neutralized with sulfuric acid and the product distilled under reduced pressure.

Quantities Methyl methoxy acetate 160 parts, 2.5 moles Ethylene glycol parts, 2.5 moles Sodium methoxide (catalyst) (30% in methanol) 2 parts Product Wield substantially quantitative. Colorless liquid.

B. P. 141-142" C./25 mm.

Sp. gr. 1.174 60/60 F.

Sap. No. 420.

EXAMPLE X.-ETHYLENE BIS-METHOXY ACETATE Procedure same as for Example IX.

Quantities Methyl methoxy acetate 520 parts, 5.0 moles Ethylene glycol 155 parts, 2.5 moles Sodium methoxide (catalyst) (30% in methanol) 2 parts Product Yield substantially quantitative. Colorless liquid.

B. P. 176-77 C./25 mm.

Sp. gr. 1.194 60/60 F.

Sap. No. 555.

EXAMPLE XI.54 arts of glycerol beta methyl ether, 312 parts of methyl methoxy acetate, and 5 parts of a 30% solution of sodium methoxide in methanol were refluxed at atmospheric pressure (although by adjusting the pressure a similar reaction can be carried out at reflux temperature ranging between 20 and200 C.) and during the refluxing methanol of reaction was distilled from the mixture. The catalyst was removed-'1 by filtration after treatment with CO2 and-the resultingproduct fractionally distilled. Mono methoxy acetate 'of glycerol beta methyl ether, CHsOCI-IzCOOCI-Iz'GH-(OCI-I) CH2OH' was obtained in a 45% yield-based on the ester. This compound, which is a water whiteliquid, miscible in water'and' methanol; had a boiling point of -130to- 140"C. at 3- mm pressure'. Bimethoxy acetate of glycerol beta methyl ether,

This compound was likewis water White coholysis catalysts, e. g., sulfuric, p. toluene sulphonic acid, and hydrochloric acids, may be employed.

The polyhydric alcohol esters and.ether.-esters of glycclic acid, as well as the other esters described herein, have many characteristics which particularly fit them for uses in the arts. They are all generally useful assolventsor plasticizers for many natural and synthetic resins which are used withv or without pigments, fillers, extenders and the like,.which compositionsare employed for the preparation. of lacquers,.pigments, paste pigments, etc., or for the formation of films, filaments, rods, tubes, or shaped articles. More specifically, they are generally useful as solvents, plasticizers and softeners for natural resins, such, for example, as dammargcopal, kauri and for the synthetic resins, such, for example, as thealkyds; cumarone-indene; chlorinated diphenyl; soluble types of polymerized hydrocarbons, phenol-formaldehyde and urea-formaldehyde resins; ester. gum; polymeric acrylic and methacryliczacids and their esters, amides, nitriles, imid'es;,saits', interpolymers, and other derivatives; polyvinyl alcohol; the polyvinyl esters; styreneandfotherpolymeric resins, as well as simple mixturesof' the natural and/or synthetic resins, and/or. inter- I polymers of they polymeric resins. The polyhydroxy alcohol esters ofglycolic acidare also useful as solvents, plasticizers or softeners of regenerated cellulose and the cellulose derivatives, such as, cellulose acetate,- nitrate, aceto-nitrate, aceto-propionate, methylcellulose, ethyl cellulose and other organicderivatives of' cellulose or'mixtures thereof.

The polyhydric alcohol esters of glycolic acid are likewise generally applicable as the major ingredients in the preparation of printing, pads and ink feeders of all types, as penetrating agents for printing pastes, and as major'ingredients" in the preparation of inks, bothior-v thegprinting. of paper, textiles, wood, metal or other materials:

The ethylene glycol monoglycolate, diglycolate andglycerol mono-, diand tri'-glycolate, may be used as softeners for glassine paper, asa substitute forglycerine in tobacco, as aisoftener for regenerated cellulose and as: a substitute for glycerol in printing ink compositions. They have likewise been found acceptable for the sizing of the artificial andnatural silks and" particularly for the sizing of regenerated; cellulose' filaments.

and fabrics and" are also most" efiective'as softening agents for cotton, wool, linen, jute, rayon and silk.

Glycolate esters of the alkyl ethers of polyhydric alcohols such, for example, as gl'ycoll'c acid esters of themonoalkyl ethers of ethylene glycol, HOCHzCOOCI-IzCHa'OR', are, as has been generally stated above, excellent solvents for cellulose ethersandcellulose' esters. These compositions are'especially valuable in brush-type lacquers and lacquers applied hot, as they improve the flow and gloss properties of. the resulting films. The ether-esters havebeen .found acceptable .as frothing agents for the flotation of ores and as solvents for the absorption of. acidic gasessuch as the sulfur oxides, hydrogen-sulfideaetc. Furthermore, they, together with the other polyhydric alcohol esters of glycolic acid, are excellentsolvents and liquid media for certain dyestuffs and pigments wherein they may be substituted for theethers '01 the polyhydric alcohols.

'I'hepolyhydric alcohol esters. and ether-esters of glycolic acids, hereinbefore described, may also be used as ingredients in the preparation of compounds for defrosting and anti-misting; in cosmetic preparations; as dye solventslfor basic acid and direct dyes; asthe fluid medium for electrolytic condensers; as ingredients in leather finishes and varnish removers; as solvents and fixatives for perfumes; as softeners for cork binders, glue, gelatin, paper: and textilesizes; as an ingredient in dentifrice compositions; as softeners for casein; zein, soybean,.protein plastics, etc.; asan-ingredient in leak-proofing compositions for gas distributing systems, gas masks and the like; in

the preparation of wetting, dispersing and. pene- .lent. solventi properties: of. materials of this type can. be attributed; to the combination of ether and; ester groupings.

All glycolate esters disclosed can be-reacted' with an aliphaticor aromatic anhydride or acid to. givezrelatively water insoluble esters that are good plasticizer-softeners glycerol glycolates reacted' with' acetic anhydride will givethe triacetatesof the three glycolates of glycerol. I 1 K From aconsideration of-the above specification it. will be realized that 'manychanges may be made in the details therein given without departing from the scopeof the invention or sacrificing any of "the-a'dvantages that may, be derived therefrom;

We claim:

1. A process which comprises alcoholysisof a lower (alkyl). ester of acetic acid having. the empirical formula, ROCHZ'CO'OH, in which R is a radical selectedfrom' the. group. consisting of hydrogen,,. alkyl, and alkoxy-alkylene groups,

witha compound selected from thegroup consisting of'glyc'erol' and alkyllethers. thereof; 7

2;A process which comprises alcoholysis of a 'As an example the substituted acetic acid ester of a lower aliphatic alcohol having the empirical formula,

RCHzOCHzCOOX,

a lower alkyl hydroxy acetate with glycerol to,

form a glycerol hydroxy acetate.

5. A process which comprises the alcoholysis of a lower (alkyl) alkoxy acetate,

alkylOCI-lzCOO-alkyl,

with glycerol to form a glycerol alkoxy acetate.

6. A process which comprises the alcoholysis of a lower (alkyl) alkoxy acetate,

alkylOCHzCOO-alkyl,

with 2. glycerol ether to form an alkoxy acetate of a glycerol ether.

7. A process which comprises the alcoholysis of methyl hydroxy acetate with glycerol to obtain glycerol mono glycolate.

8. A process which comprises the alcoholysis of I methyl lycolate with glycerol mono glycolate to obtain glycerol di glycolate.

9. A process for the preparation of mono and di methoxyacetate of glycerol beta methyl ether which comprises alcoholysis of methyl methoxy acetate with glycerol beta methyl ether.

10. A process for the preparation of glycerol mono glycolate which comprises reacting under reflux approximately equimolecular proportions of methyl glycolate and glycerol in the presence of anhydrous potassium carbonate as the catalyst, distilling off the methanol formed as the result of the reaction, and recovering the glycerol mono glycolate from the reaction product.

11. A process for the preparation of glycerol diglycolate which comprises reacting approximately equimolecular proportions of glycerol mono glycolate and methyl glycolate in the presence of anhydrous potassium carbonate as the catalyst, continuing the reaction until substantially no more methanol distills over, and recovering from the reaction product the glycerol diglycolate formed.

12. A process for the preparation of mono and di methoxy acetate of glycerol beta methyl ether which comprises reacting under reflux approximately 54 parts of glycerol beta methyl ether with approximately 312 parts of methyl methoxy acetate in the presence of 5 parts of a 30% methanol solution of sodium methoxide, withdrawing during the reaction the methanol formed, destroying the catalyst by the addition of carbon dioxide, filtering the resulting solution free from the precipitated catalyst and subsequently recovering the mono and di methoxy acetates of glycerol beta methyl ether from the resulting product.

13. Glycerol mono glycolate, having the em pirical formula HOCH2COOCH2.CHOH.CH2OH having a specific gravity of 1.32 at 60 C./60 C.

DONALD J. LODER.

O- ET Rfi 

